|Publication number||US4965231 A|
|Application number||US 07/266,735|
|Publication date||Oct 23, 1990|
|Filing date||Nov 3, 1988|
|Priority date||Nov 3, 1988|
|Also published as||CA1330569C|
|Publication number||07266735, 266735, US 4965231 A, US 4965231A, US-A-4965231, US4965231 A, US4965231A|
|Inventors||Pankaj K. Mehrotra, Elizabeth R. Billman|
|Original Assignee||Kennametal Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (31), Non-Patent Citations (43), Referenced by (14), Classifications (14), Legal Events (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The present invention relates to alumina based ceramic compositions containing zirconia and silicon carbide. It especially relates to ceramic articles useful in high temperature (600° C. to 1200° C.) wear applications.
In the past, zirconia has been added in specified amounts to selected alumina-silicon carbide whisker reinforced compositions described in U.S. Pat. Nos. 4,534,345 and 4,507,224 to provide enhanced fracture toughness and/or flexural strength (see: U.S. Pat. Nos. 4,657,877 and 4,749,667; Japanese Patent Publication No. Sho 62-265182; Clausen et al, "Whisker-Reinforced Oxide Ceramics," Journal de Physique Colloque Cl, Supplement au No. 2, Tome 47, February 1986, Pages Cl-693 to Cl-702; Becher et al, "Toughening of Ceramics by Whisker Reinforcement," Fracture Mechanics of Ceramics 7, ed. by Bradt et al, Plenum Press, New York (1986), Pages 61-73).
It has been indicated that the zirconia should be in the monoclinic and/or (metastable) tetragonal phase to obtain improved fracture toughness and/or flexural strength. It has been further indicated that the metastable tetragonal phase is obtained by reducing zirconia particle size or through the use of a cubic zirconia stabilization promoter such as yttria, calcia, magnesia and the rare earth oxides in amounts below that required to fully stabilize the cubic zirconia phase.
Cutting tools composed of a variety of compositions containing alumina, zirconia and silicon carbide whiskers with or without other additives have been proposed (see: European Patent Application No. 86107916.8 (published Jan. 21, 1987 as No. 0208910); U.S. Pat. No. 4,749,667; "Multitoughening Ceramic," Techno Japan, Vol. 19, No. 10, October 1986, Page 78; and European Patent Application No. 86301597.0, published Sept. 17, 1986, as No. 0194811).
Where an indication is given as to the material being cut by these tools, these tools have been applied to the machining of cast irons, hardened steels and nickel based superalloys. These are all materials that have relatively low reactivity with the silicon carbide in the cutting insert at the high temperatures encountered during metalcutting. None of the foregoing documents teaches or suggests that, for metalcutting inserts for use in the high speed roughing of soft steels, cutting performance can be significantly improved by controlling the alumina based ceramic composition to within the combination of critical ranges now discovered by the applicants for zirconia, magnesia, silicon carbide and tetragonal zirconia contents.
Applicants have surprisingly discovered that alumina based ceramic compositions containing (in volume percent, v/o) about 1.5 to 17.5 v/o silicon carbide whiskers, about 5 to 17.5 v/o zirconia, the residue of a magnesium oxide or other magnesium-oxygen compound addition, and at least 4 v/o tetragonal zirconia, have excellent high temperature wear properties as indicated by excellent cutting edge lifetimes when engaged in the high speed rough machining of soft steel. It has been surprisingly found that, despite the finding that minor magnesia additions act to reduce the amount of tetragonal (i.e., metastable tetragonal) zirconia at room temperature, an effective amount of this addition has a significant positive affect on cutting edge lifetime in the high speed rough turning of soft steels, such as AISI (American Iron and Steel Institute) 1045 steel.
In accordance with the present invention, it has been surprisingly found that the magnesia addition can be added to the present composition in amounts effective to preferably provide the cutting edge with a lifetime of at least 12 minutes when turning AISI 1045 steel, having a Brinell hardness number in the range of 190 to 200, under the conditions of 1000 surface feet/minute, 0.025 inch/revolution and 0.100 inch depth of cut. These magnesia additions, more preferably, can produce cutting edge lifetimes of at least 15, and most preferably, of at least 20 minutes. It is preferred that magnesia be added in amounts of about 0.03 to 3 v/o; more preferably, about 0.03 to 2.0 v/o; and most preferably, about 0.04 to 1.0 v/o.
Preferably, the alumina based ceramic composition according to the present invention contains about 2.5 to 15 v/o and, more preferably, about 2.5 to 10.5 v/o silicon carbide whiskers.
The zirconia content according to the present invention is preferably 7.5 to 17.5 v/o and, more preferably, about 10 to 15 v/o. In accordance with the present invention, a significant fraction of the zirconia (preferably at least 22 volume percent) is in the form of tetragonal zirconia and must form at least 4 v/o of the composition. Preferably, at least 6 v/o; more preferably, at least 7 v/o; and most preferably, at least 8 v/o of the composition is in the form of tetragonal zirconia.
These and other aspects of the present invention will become more apparent upon review of the detailed description of the present invention in conjunction with the figures briefly described below:
FIG. 1 is an isometric view of an embodiment of a square cutting insert in accordance with the present invention.
FIG. 2 shows a graph of the volume percent tetragonal zirconia in the composite as a function of the volume percent of magnesia, or yttria, addition.
In a preferred embodiment of the present invention, as shown in FIG. 1, a metalcutting insert 10, preferably of the indexable type, is provided having a rake face 30, a flank face 50 and cutting edge 70 at the juncture of the rake and the flank faces. The cutting edge 70 is preferably in a chamfered condition (e.g., K-land) as shown in FIG. 1. The metalcutting insert is composed of an alumina based ceramic composition containing: about 1.5 to 17.5 v/o silicon carbide whiskers; about 5 to 17.5 v/o zirconia; and a residue of a magnesium oxide or other magnesium-oxygen compound addition added in an amount effective to enhance the metalcutting lifetime of the cutting edge when engaged in the high speed rough turning of a soft iron base alloy, such as AISI 1045 steel having a hardness of about 190 to 200 BHN (Brinell Hardness Number). The silicon carbide whiskers zirconia and residue of magnesia are substantially homogeneously distributed in an alumina based matrix.
The silicon carbide whiskers are present at a level of at least about 1.5 v/o to assure minimal levels of cutting edge lifetime improvement. More preferably, silicon carbide whiskers are present at about 2.5 v/o or more. The silicon carbide whisker content preferably should not exceed about 17.5 v/o of the composition. We believe that silicon carbide whisker contents above this value result in a significant decrease in the cutting edge lifetime during the high speed rough turning of soft steels. Therefore, to further maximize cutting edge lifetime during high speed roughing of steels, such as AISI 1045, it is preferred that the maximum content of silicon carbide whiskers be held at or below about 15 v/o and, more preferably, at or below about 10.5 v/o of the alumina based ceramic composition.
The silicon carbide whiskers utilized herein may be any of the commercially available brands which have been used in the past in alumina based metalcutting inserts for machining nickel base superalloys.
While less preferred, silicon carbide particles of a generally equiaxed shape or platelet shape may be substituted for part of the silicon carbide whiskers in this invention.
The zirconia content is in the range of about 5 to 17.5 v/o of the ceramic composition. Zirconia contents outside of this range are believed to provide compositions having reduced cutting edge lifetime during the high speed roughing of AISI 1045 steel. Preferably, to maximize cutting edge lifetime, the zirconia content should be within the range of about 7.5 to 17.5 v/o and, more preferably, about 10 to 15 v/o of the composition. While we believe that the concentration of tetragonal zirconia should be maximized for best cutting performance, it is equally, if not more, important in our opinion that as much of the tetragonal zirconia as possible, present at room temperature, be available for transformation toughening at, or as near as possible to, the temperatures encountered at the cutting edge during machining. It is, therefore, critical to the present inVention that magnesia be present in certain small, but effective, amounts which have been found critical to the maximization of cutting edge lifetime. In accordance with the present invention, at least about 22 volume percent of the zirconia present, and at least 4 v/o of the ceramic composition, must be tetragonal zirconia. Preferably, the tetragonal zirconia forms at least about 6 v/o of the composition, more preferably, at least about 7 v/o of the composition, and most preferably, at least about 8.0 v/o of the composition.
Magnesia additions, despite the fact that they decrease the amount of tetragonal zirconia observed at room temperature, are preferably added in the range of about 0.03 to 3 v/o of the composition, more preferably, about 0.03 to 2 v/o; most preferably, about 0.04 to 1.0 v/o. Magnesia may be blended in with the alumina or zirconia just prior to compact pressing, or it may be preblended or prealloyed with the alumina or zirconia. Preblending of the magnesia powder is preferred since it is believed that the preblended magnesia is more effective in producing high temperature metastable tetragonal zirconia, thus allowing a smaller amount of magnesia to be added and minimizing the deleterious effects of high magnesia additions (e.g., lower melting point glass and Mg-Al-0 formations). Equivalent amounts of other magnesium-oxygen compounds, such as magnesium carbonate, which may require an additional processing step such as calcination to produce magnesia may be substituted for all or part of the magnesia addition. After sintering of the blended compositions, the magnesia addition may not exist as a separate phase but as a residue. This residue may include, for example, magnesia-alumina solid solution, magnesium aluminate, a magnesia zirconia solid solution and/or a glass, for example, formed with silicon dioxide impurities which may have existed as a thin coating on the silicon carbide whiskers.
The remainder of the ceramic composition is essentially alumina and preferably entirely alumina except for impurities. In all cases, the present alumina based ceramic composition contains at least 40 v/o alumina and, preferably, at least about 50 v/o alumina.
Titanium carbide, as whiskers and/or substantially equiaxial particulate, may be added in an amount of about 2 to 35 v/o of the composition and, preferably of about 10 to 30 v/o. Titanium carbide has a higher thermal expansion coefficient than alumina. It is, therefore, believed that titanium carbide additions should allow more tetragonal zirconia to be retained at room temperature. Titanium carbide whiskers may be manufactured and harvested by the methods described in A. Kato et al, "Growth Rate of Titanium Carbide Whiskers in Chemical Vapor Deposition," J. Cryst. Growth. 37 (1977), Pages 293-300; and N. Tamari et al, "Catalytic Effects of Various Metals and Refractory Oxides on the Growth of TiC Whiskers by Chemical Vapor Deposition," J. Cryst. Growth, 46 (1979), pages 221-237. Titanium carbide whiskers and their incorporation and use in alumina based cutting inserts are disclosed in Mehrotra et al U.S. Patent Application Ser. No. 056,091, filed May 28, 1987, and assigned to Kennametal Inc. now U.S. Pat. No. 4,852,999.
The alumina powders utilized herein should be high purity alumina (i.e., >99% pure) such as produced by ALCOA (e.g., grade A16SG), by Ceralox (e.g., grade HPA - 0.5 with or without magnesia) or by Reynolds Chemicals (grade RC-HP or RC-HP-DBM).
Yttria, calcia, the rare earth oxides, and other compounds which have, through a reduction in the tetragonal to monoclinic transformation temperature, an adverse affect on cutting edge lifetime are preferably present only as impurities, if present at all.
The foregoing material, in accordance with the present invention, may be milled, blended, and densified at high temperature to produce at least 98%, and preferably, at least 99% dense alumina based ceramic compositions having an alumina based matrix, which is preferably entirely alumina, in which the silicon carbide, magnesia residue from the magnesia addition, zirconia and titanium carbide, if any, are at least substantially homogeneously distributed. Hot pressing or sintering temperatures are preferably held below 1700° C., and more preferably, below 1650° C. and, most preferably, below about 1600° C. to minimize zirconia particle growth and thereby maximize the tetragonal zirconia phase present in the final product. The average zirconia particle size in the cutting insert should not exceed about 5 microns, preferably should not exceed 2 microns, and more preferably, should not exceed 1 micron. However, the average zirconia particle size should be large enough to allow most tetragonal zirconia to transform to monoclinic zirconia during use. This minimum size will depend upon the ceramic composition and is presently undetermined.
Preferably, the material in accordance with the present invention has a Rockwell A hardness of at least 93 and a KIC (E & C) toughness of at least about 5MPam1/2.
While not wishing to be bound by any particular theory, applicants offer the following explanation of the present invention. In alumina-silicon carbide whisker-zirconia compositions, the amount of metastable tetragonal zirconia that can be obtained at room temperature can be increased by a reduction in zirconia particle size or the addition of the so-called cubic stabilizing agents, such as yttria, calcia and/or the rare earth oxides. (see: Stevens, "An Introduction to Zirconia--Zirconia and Zirconia Ceramics," Magnesium Elektron Pub. No. 113, Magnesium Elektron Ltd., England (1986)). While the literature commonly includes magnesia among the foregoing list of stabilizing agents, applicants have found that, when magnesia is added in the amount of about 0.03 to 3 v/o to the present compositions, magnesia decreases the amount of tetragonal zirconia present at room temperature. When yttria is added to zirconia, it tends to stabilize the tetragonal and cubic phases of zirconia to a lower temperature. All the aforementioned stabilizing agents, and most impurities, except for magnesia, affect ZrO2 in similar ways (i.e., they reduce the temperature at which the tetragonal zirconia phase is stable). At room temperature, some of the zirconia may be present as metastable tetragonal zirconia. Under the action of tensile stress, this tetragonal zirconia may become monoclinic, giving rise to transformation toughening. However, as the temperature increases, tetragonal zirconia becomes stable and, therefore, unavailable for transformation to the monoclinic crystal structure. Thus, any impurity or additive, such as yttria, which stabilizes tetragonal zirconia at lower temperatures, is unsuitable for metalcutting applications since the cutting tip temperature may rise to 1000 °to 1200° C. in high speed machining. Therefore, in accordance with the theory of the present invention, additives which raise the monoclinic to tetragonal transformation temperature of the zirconia are required for high temperature transformation toughening. We have found that there are only two oxide additives, MgO and HfO2, which raise the transformation temperature. Thus, we believe that by keeping the zirconia particle size small, a large proportion of the zirconia can be retained as metastable tetragonal zirconia at the high temperature of metalcutting by allowing the zirconia with magnesia or hafnia. It is our belief that this helps to obtain enhanced tool lives in metalcutting operations. It should be noted that zirconia normally contains up to about 2 w/o (weight percent) hafnia as an impurity.
The significant positive impact that magnesia additions have on metalcutting performance is more clearly indicated by the following examples which are purely illustrative of the present invention.
Six compositions were prepared (Table 1) with the nominal compositions being Al2 O3 - 10 v/o SiCw (silicon carbide whiskers) - 10 v/o ZrO2. Small additions of Y2 O3 and MgO were made. In the case of Mix No. 6, about 0.05 w/o (approximately 0.06 v/o) MgO had already been blended with Al2 O3 by the powder manufacturer. This provided Mix No. 6 with a magnesia content of about 0.04 v/o. Fifty gram batches of these powders were prepared by first blending Al2 O3 and ZrO2 (and stabilizing additives, if any) slurries (propanol) in a jar mill using Al2 O3 cycloids for one hour. Sonicated SiCw slurry was then added, and the whole mix was blended for one hour. Al2 O3 and ZrO2 slurries had previously been milled to obtain mean particle sizes of 0.5 to 0.6 μm and 0.6 to 0.8 μm, respectively (corresponding specific surface areas measured by BET were 10 to 14 m2 /g and 20 to 40 m2 /g, respectively). Then, the mix was pan dried, screened through 100 mesh screen, and hot pressed in a one inch diameter graphite die at the temperatures and pressures shown below in Table 1 for one hour in argon. The resulting billets were more than 99% dense, and were cut, ground and polished for measurement of physical and mechanical properties. The billets were also cut and ground to produce indexable cutting inserts for metalcutting tests.
TABLE 1______________________________________COMPOSITIONS______________________________________Nominal Composition: Al2 O3 - 10 v/o SiCw - 10 v/oZrO2Al2 O3 Alcoa A16SGSiCw Tokai Carbon Co. (Tokyo, Japan) TOKAWHISKER (TOKAMAX) Grade 1 (0.3-1.0 μm diameter; 20-50 μm length)ZrO2 Zircar - unstabilizedMgO Fisher Scientific Corp. - Reagent Grade BET = 40.4 m2 /gY2 O3 MolyCorp, BET = 15.4 m2 /gHot PressingMix No. Temp.(°C.) Pressure (psi) Composition______________________________________1. 1650 4000 Nominal2. 1650 4500 Nominal + 1 v/o Y2 O33. 1625 4500 Nominal + 1 v/o MgO4. 1600 4500 Nominal + 1 V/o Y2 O3 + 1 v/o MgO5. 1625 4500 Nominal, except that Al2 O3 used was Ceralox Grade HPA - 0.5 (0.5 to 0.7 μm median particle size)6. 1625 4500 Nominal, except that Al2 O3 used was Ceralox Grade HPA - 0.5 with MgO (0.05 w/o)______________________________________
TABLE 2______________________________________PROPERTIES Tetragonal ZrO2 2Mix RA Fracture Toughness as v/o as v/o ofNo. Hardness KIC (E&C)1 (MPa m1/2) of ZrO2 Composite______________________________________1 93.3 5.59 84 8.42 93.3 4.97 100 103 93.6 5.96 70 74 93.6 4.63 98 9.85 93.9 5.88 84 8.46 93.8 5.88 76 7.6______________________________________ 1 Evans and Charles, "Fracture Toughness Determination by Indentation," J. American Ceramic Society, Vol. 59, No. 7-8, Pages 371, 372, using an 18.5 kg load. 2 As measured by xray diffraction of a polished surface. The remainder of the zirconia is assumed to be monoclinic zirconia. Cubic zirconia, which may be present in minor amounts, is included within the tetragonal zirconia estimate.
Physical and mechanical properties of the hot pressed composites are shown in Table 2.
The Porter-Heuer (Porter et al, J. American Ceramic Society, Vol. 62, No. 5-6 (1979), pages 298-305) formula was modified and used to estimate the fraction of monoclinic ZrO2 (Vm) from peak intensities of the 111 reflection of the monoclinic ZrO2 (Im(111)), and 111 reflection of the tetragonal ZrO2 (It(111)): ##EQU1## where Vt is the fraction of ZrO2 which is tetragonal ZrO2.
The estimated volume fraction of tetragonal ZrO2 in the whole composite is (vt):
vt=Vt vz (3)
where vz is the volume fraction of the total ZrO2 added in the mix. The above relationship assumes that ZrO2 substantially remains unchanged during consolidation except for the phase transformations discussed above.
FIG. 2 shows the effect of the various additives on the amount of tetragonal zirconia in the composites. It can clearly be seen that magnesia additions lower the amount of tetragonal zirconia (curve 1), whereas, yttria additions increase the amount of tetragonal zirconia at room temperature (curve 2).
TABLE 3______________________________________ TURNING AISI 1045* STEEL (192-200 BHN)______________________________________Insert Cutting Edge Life & Average LifeMaterial Failure Mode (minutes)______________________________________Mix 1 14. BK 14.7 BK 14.4Mix 2 8. BK 12.6 BK 10.3Mix 3 15.9 BK 29.2 FW 22.6Mix 4 1.7 FW 7.7 FW 4.7Mix 5 17. FW 7.5 BK 12.3Mix 6 22.9 DN 32.9 FW 27.9______________________________________Test Conditions:1000 sfm (surface feet/minute)0.025 ipr (inch/revolution)0.100 inch doc (depth of cut)SNGN-453T (American National StandardDesignation in accordance with ANSI B212.4 - 1986) indexablecutting insert style(cutting edge preparation:0.008 inch × 20° K-land)15° lead angle (side cutting edge angle)-5° side rake angle-5° back rake angleno coolantCutting Edge Life Criteria:FW - .015" uniform flank wearMW - .030" concentrated flank wearCR - .004" crater wearDN - .030" depth of cut notchCH - .030" concentrated wear or chippingBK - breakage*AISI 1045 is equivalent to Unified Numbering System (UNS) Designation -G10450.
Indexable insert cutting edge lifetimes in the high speed roughening of a premachined AISI 1045 steel are shown in Table 3. It can be clearly seen that a significant improvement in cutting edge lifetime is achieved by the addition of magnesia, whereas, a decrease in tool life occurs when yttria is added despite the high level of tetragonal zirconia present in the yttria containing compositions.
TABLE 4______________________________________COMPOSITIONS______________________________________Nominal Composition: Al2 O3 - 5 v/o SiCw - 10 v/oZrO2Al2 O3 Ceralox - HPA - .5 without MgOSiCw Tokai Grade 1ZrO2 Magnesium Elektron (SC15) - unstabilized (.5-.6 μm particle size BET 5-8 m2 /g)______________________________________Hot PressingMix No. Temp. °C. Pressure(psi) Composition______________________________________7 1535° C. 5000 psi Nominal + .05 v/o MgO8 1550° C. 5000 psi Nominal + .25 v/o MgO9 1550° C. 5000 psi Nominal + .50 v/o MgO10 1550° C. 5000 psi Nominal + 1.0 v/o MgO11 1550° C. 5000 psi Nominal + 3.0 v/o MgO______________________________________
A second series of mixes, 7 to 11 shown in Table 4, were made to further demonstrate the effect that the level of the magnesia has on tetragonal zirconia content and cutting edge lifetime. All samples were processed and hot pressed essentially as described with respect to the samples produced from Mixes 1 to 6.
The physical and mechanical properties of the materials are reported in Table 5. It can clearly be seen that the tetragonal zirconia content again clearly decreases with increasing amounts of magnesia addition. This affect is also shown in FIG. 1, curve 3. It can be seen that Mixes 7 to 11 have a higher tetragonal zirconia content than that found in the materials represented by curve 1. The affect is believed to be due to the lower SiCw content (5 v/o versus 10 v/o) used in the second group of mixes. Applicants have observed that generally, as SiC whisker content increases, the amount of tetragonal zirconia decreases for a given zirconia content, and everything else being held constant.
TABLE 5______________________________________PROPERTIES Tetragonal ZrO2 asMix RA Fracture Toughness v/o ofNo. V/o MgO Hardness KIC (E&C) (MPa m1/2) Composite______________________________________7 0.05 93.5 5.57 8.58 0.25 93.4 5.00 8.19 0.50 93.3 5.06 8.010 1.0 93.4 4.75 7.611 3.0 93.5 4.98 7.3______________________________________
Indexable insert cutting edge lifetimes in the high speed roughing of AISI 1045 steel are shown in Table 6.
TABLE 6______________________________________TURNING AISI 1045 STEEL (197-199 BHN)Insert Cutting Edge Life Average LifeMaterial & Failure Mode (Minutes)______________________________________Mix 7 19 bk 5 ch/bk 12 8 12.6 dn/ch 1 bk 6.8 9 12.3 dn 14.1 dn 13.210 9.7 bk 7.1 dn 8.411 7.0 bk 6.8 dn 6.9______________________________________
The test procedures and conditions and cutting edge life criteria used to generate the data shown in Tables 5 and 6 were the same as that described for Tables 2 and 3.
In another example in accordance with the present invention, a composition containing Al2 O3 -2.5 v/o SiCw -10v/o ZrO2 -1.05 v/o MgO was made. A fifty gram batch of this composition was prepared by first blending an Al2 O3 (Ceralax Grade HPA-0.5 with MgO (0.05 w/o)), ZrO2 (Magnesium Elektron SC15) and MgO (Fisher Reagent Grade) slurry (propanol) in a jar mill using Al2 O3 cycloids for one hour. A Sonicated SiCw (Tokai Grade 1) slurry was then added and the whole mix was blended for one hour. The Al2 O3 and ZrO2 containing slurries had previously been milled to obtain mean particle size of about 0.5-0.7 μm and 0.5 to 0.6 μm, respectively. Then the mix was pan dried, screened through a 100 mesh screen and isostatically compacted at 30,000 psi at room temperature. Pieces were then cut from the resulting cold compacted blank and sintered at 1700 degrees Centigrade for one hour in one atmosphere argon followed by hot isostatic pressing at 1600 degrees Centigrade for one hour in 17,000 psi argon. The resulting samples were greater than 99 percent dense (i.e., fully dense). As described in the prior examples, samples were then prepared for physical and mechanical testing and ground into indexable cutting inserts. It was determined that the samples contained about 6.6 v/o tetragonal zirconia. It is estimated that material processed in this manner has a zirconia particle size of about 5 μm or less. Cutting inserts of the style described in Table 3 were tested under the conditions used in Table 3. Cutting edge life times of 14.4 (DN failure) and 18.9 (FW & CH failure) minutes were obtained.
It is believed that cutting edge lifetime may be extended or made more uniform if the cutting edge is honed and/or the insert surface is lapped or polished to remove surface material containing a higher percentage of monoclinic and a lower percentage of tetragonal zirconia than is characteristic of the bulk of the material (i.e., a polished surface). It is known that grinding stresses create a surface layer in which a portion of the metastable tetragonal zirconia has been transformed to monoclinic zirconia. It is preferred that at least those surface areas of the insert which will encounter high temperatures during use have the maximum amount of tetragonal zirconia available for high temperature transformation.
All patents, patent applications and documents referred to herein are hereby incorporated by reference.
Other embodiments of the invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US4218253 *||Oct 2, 1978||Aug 19, 1980||Feldmuhle Aktiengesellschaft||Sintered ceramic material of improved ductility|
|US4292049 *||May 27, 1980||Sep 29, 1981||Ngk Spark Plug Co., Ltd.||Ceramic materials for high-speed cutting|
|US4298385 *||Jul 14, 1980||Nov 3, 1981||Max-Planck-Gesellschaft Zur Forderung Wissenschaften E.V.||High-strength ceramic bodies|
|US4316964 *||Jul 14, 1980||Feb 23, 1982||Rockwell International Corporation||Al2 O3 /ZrO2 ceramic|
|US4331048 *||May 30, 1980||May 25, 1982||Feldmuhle Aktiengesellschaft||Cutting tip for metal-removing processing|
|US4366254 *||May 1, 1981||Dec 28, 1982||The Valeron Corporation||High toughness ceramic cutting tool|
|US4419311 *||Jul 6, 1981||Dec 6, 1983||Nils Claussen||Production of high-strength ceramic bodies of alumina and unstabilized zirconia with controlled microfissures|
|US4421861 *||May 19, 1980||Dec 20, 1983||Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften E.V.||High-strength and temperature-change resistant ceramic formed body, especially of mullite, its production and use|
|US4506024 *||Sep 1, 1983||Mar 19, 1985||Max-Planck-Institut Zur Foerderung Der Wissenschaften E.V.||Ceramic formed body with a high crack arrestability|
|US4507224 *||Nov 30, 1983||Mar 26, 1985||Agency Of Industrial Science & Technology||Ceramics containing fibers of silicon carbide|
|US4543343 *||Feb 28, 1984||Sep 24, 1985||Hitachi Metals, Ltd.||Ceramics for cutting tools|
|US4543345 *||Feb 9, 1984||Sep 24, 1985||The United States Of America As Represented By The Department Of Energy||Silicon carbide whisker reinforced ceramic composites and method for making same|
|US4657877 *||May 21, 1986||Apr 14, 1987||The United States Of America As Represented By The United States Department Of Energy||Silicon carbide whisker-zirconia reinforced mullite and alumina ceramics|
|US4745091 *||Aug 11, 1986||May 17, 1988||Landalloy, Inc.||Novel compositions for oxide ceramics|
|US4746635 *||May 19, 1986||May 24, 1988||Kabushiki Kaisha Riken||High strength and high hardness alumina-zirconia-silicon carbide sintered ceramic composite and its manufacturing process|
|US4749667 *||Feb 3, 1987||Jun 7, 1988||Carboloy Inc.||Alumina - zirconia ceramics reinforced with silicon carbide whiskers and methods of making the same|
|US4767727 *||May 23, 1986||Aug 30, 1988||Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V.||Fibre-strengthened ceramic formed bodies|
|US4770673 *||Oct 9, 1987||Sep 13, 1988||Corning Glass Works||Ceramic cutting tool inserts|
|US4789277 *||Feb 23, 1988||Dec 6, 1988||Advanced Composite Materials Corporation||Method of cutting using silicon carbide whisker reinforced ceramic cutting tools|
|US4801510 *||Sep 2, 1987||Jan 31, 1989||Kennametal Inc.||Alumina coated silcon carbide whisker-alumina composition|
|US4820663 *||Sep 2, 1987||Apr 11, 1989||Kennametal Inc.||Whisker reinforced ceramic and a method of clad/hot isostatic pressing same|
|US4849381 *||Jun 3, 1988||Jul 18, 1989||Sandvik Ab||Ceramic cutting tool with improved toughness behavior|
|US4852999 *||May 28, 1987||Aug 1, 1989||Kennametal Inc.||Cutting tool|
|US4867761 *||Mar 18, 1988||Sep 19, 1989||Sandvik Ab||Ceramic cutting tool reinforced by whiskers|
|EP0194811A2 *||Mar 6, 1986||Sep 17, 1986||Advanced Composite Materials Corporation||Reinforced ceramic cutting tools|
|EP0202504A2 *||Apr 25, 1986||Nov 26, 1986||Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V.||Composite ceramic|
|EP0208910B1 *||Jun 10, 1986||Apr 12, 1989||NGK Spark Plug Co. Ltd.||Fiber-reinforced compositie material for tools|
|EP0252046A2 *||Jun 16, 1987||Jan 7, 1988||Sandvik Aktiebolag||Coated ceramic sintered whisker reinforced body|
|JPS6330378A *||Title not available|
|JPS62265182A *||Title not available|
|WO1986005480A1 *||Mar 13, 1986||Sep 25, 1986||Atlantic Richfield Company||High density reinforced ceramic bodies and method of making same|
|1||"60 Year Old Grows Whiskers," Metal Powder Report, Jul. 1986.|
|2||"Feldmuehle SPK Tools Fast & Safe," advertisement (9/1981).|
|3||"Multitoughening Ceramic," Techno Japan, vol. 19, No. 10, Oct. 1986.|
|4||"Phase Diagrams for Ceramists," Amer. Cer. Soc. (1975 Supp), pp. 117, 163E, 166.|
|5||*||60 Year Old Grows Whiskers, Metal Powder Report, Jul. 1986.|
|6||*||American National Standard for Cutting Tools, Ansi B212.4 1986.|
|7||American National Standard for Cutting Tools, Ansi B212.4-1986.|
|8||Becher et al., "Toughening of Ceramics by Whisker Reinforcement," Fracture Mechanics & Ceramics, (proceedings of Conf. held 6-19-21, 1985, Va.), ed. by Bradt et al., Plenum Press, N.Y. (1986), pp. 61-73.|
|9||Becher et al., "Transformation Toughened and Whisker Reinforced Ceramics," Soc. of Automotive Engineers, Proc. 21st Auto. Techn. Dev. Meeting, Mar. 1984, pp. 201-205.|
|10||*||Becher et al., Toughening of Ceramics by Whisker Reinforcement, Fracture Mechanics & Ceramics, (proceedings of Conf. held 6 19 21, 1985, Va.), ed. by Bradt et al., Plenum Press, N.Y. (1986), pp. 61 73.|
|11||*||Becher et al., Transformation Toughened and Whisker Reinforced Ceramics, Soc. of Automotive Engineers, Proc. 21st Auto. Techn. Dev. Meeting, Mar. 1984, pp. 201 205.|
|12||Buljan, S. T. et al., "Ceramic Whisker-and Particulate-Composites: Properties, Reliability, and Applications", Ceramic Bulletin, vol. 68, No. 2 (1989), pp. 387-394.|
|13||*||Buljan, S. T. et al., Ceramic Whisker and Particulate Composites: Properties, Reliability, and Applications , Ceramic Bulletin, vol. 68, No. 2 (1989), pp. 387 394.|
|14||Clausen et al., "Whisker Reinforced Oxide Ceramics," Journal de Physique Colloque Cl, Supplement No. 2, tome 47, Feb. 1986, pp. CL-693 to CL-702.|
|15||*||Clausen et al., Whisker Reinforced Oxide Ceramics, Journal de Physique Colloque Cl, Supplement No. 2, tome 47, Feb. 1986, pp. CL 693 to CL 702.|
|16||Clausen, "Fracture Toughness of Al2 O3 with an Unstabilized ZrO2 Dispersed Phase," Journal of the American Society, vol. 59(1-2), pp. 49-51.|
|17||*||Clausen, Fracture Toughness of Al 2 O3 with an Unstabilized ZrO 2 Dispersed Phase, Journal of the American Society, vol. 59(1 2), pp. 49 51.|
|18||Claussen et al., "Phase Transformations of Solid Solutions of ZrO, & HfO2 in AN Al2 O3 Matrix," Sci. & Tech. of Zirconia, Advances in Ceramics, vol. 3, Eds. A. H. Heuer & L. W. Hobbs, Am. Cer. Soc. (1981), pp. 164-166.|
|19||*||Claussen et al., Phase Transformations of Solid Solutions of ZrO, & HfO 2 in AN Al 2 O 3 Matrix, Sci. & Tech. of Zirconia, Advances in Ceramics, vol. 3, Eds. A. H. Heuer & L. W. Hobbs, Am. Cer. Soc. (1981), pp. 164 166.|
|20||E. L. Exner et al., "SiC Whisker Reinforced Al2 O3 ZrO2 Composites," Ceram. Eng. Sci. Proc., 9 [7-8], pp. 597-602 (1988).|
|21||*||E. L. Exner et al., SiC Whisker Reinforced Al 2 O 3 ZrO 2 Composites, Ceram. Eng. Sci. Proc., 9 7 8 , pp. 597 602 (1988).|
|22||E. R. Billman et al., "Machining with Al2 O3 -SiC-Whisker Cutting Tools," Ceramic Society Bulletin, vol. 67, No. 6, 1988, pp. 1016-1019.|
|23||*||E. R. Billman et al., Machining with Al 2 O 3 SiC Whisker Cutting Tools, Ceramic Society Bulletin, vol. 67, No. 6, 1988, pp. 1016 1019.|
|24||*||Feldmuehle SPK Tools Fast & Safe, advertisement (9/1981).|
|25||Grewe et al., "Whisker Reinforced Ceramics," Ceramic Forum Int'l, Aug./Sep. 1987, pp. 303-317.|
|26||*||Grewe et al., Whisker Reinforced Ceramics, Ceramic Forum Int l, Aug./Sep. 1987, pp. 303 317.|
|27||Gruss, W. W., "Turning of Steel with Ceramic Cutting Tools," Tool Materials for High Speed Machining, (proceedings held Feb. 25-27, 1987, Scottsdale, Az.), (1987), pp. 105-115.|
|28||*||Gruss, W. W., Turning of Steel with Ceramic Cutting Tools, Tool Materials for High Speed Machining, (proceedings held Feb. 25 27, 1987, Scottsdale, Az.), (1987), pp. 105 115.|
|29||*||Japan Ceramic News, vol. 1, No. 10 (12/10/87), pp. 1,2.|
|30||Metal Working News, Oct. 3, 1988, "Greenleaf Makes Ceramic Cutting Insert."|
|31||*||Metal Working News, Oct. 3, 1988, Greenleaf Makes Ceramic Cutting Insert.|
|32||*||Multitoughening Ceramic, Techno Japan, vol. 19, No. 10, Oct. 1986.|
|33||N. Claussen, "Stress Induced Transformation of Tetragonal ZrO2 Particles in Ceramic Matrices," Am. Cer. Soc. Journal, vol. 61, No. 1-2 (1978), pp. 85,86.|
|34||*||N. Claussen, Stress Induced Transformation of Tetragonal ZrO 2 Particles in Ceramic Matrices, Am. Cer. Soc. Journal, vol. 61, No. 1 2 (1978), pp. 85,86.|
|35||*||Phase Diagrams for Ceramists, Amer. Cer. Soc. (1975 Supp), pp. 117, 163 & 166.|
|36||Porter et al., "Microstructural Development in MgO-Partially Stabilized Zirconia (Mg-PS2)," Journal of Am. Ceramic Society, vol. 62, No. 5-6, May-Jun. 1979, pp. 298-305.|
|37||*||Porter et al., Microstructural Development in MgO Partially Stabilized Zirconia (Mg PS2), Journal of Am. Ceramic Society, vol. 62, No. 5 6, May Jun. 1979, pp. 298 305.|
|38||Stevens, "An Introduction to Zirconia-Zirconia and Zirconia Ceramics," Magnesium Elektron Ltd., (1986).|
|39||*||Stevens, An Introduction to Zirconia Zirconia and Zirconia Ceramics, Magnesium Elektron Ltd., (1986).|
|40||Tien et al., "Toughened Ceramics in the System Al2 O3 : Cr2 O3 12rO2 : HfO2 " Int. J. High Tech. Ceramics 2 (1986), pp. 207-219.|
|41||*||Tien et al., Toughened Ceramics in the System Al 2 O 3 : Cr 2 O 3 12rO 2 : HfO 2 Int. J. High Tech. Ceramics 2 (1986), pp. 207 219.|
|42||Whitney, E. D. et al., "Engineered Ceramics for High Speed Machining," (proceedings Feb. 25-27, 1987, Scottsdale, Az.) (1987), pp. 77-82.|
|43||*||Whitney, E. D. et al., Engineered Ceramics for High Speed Machining, (proceedings Feb. 25 27, 1987, Scottsdale, Az.) (1987), pp. 77 82.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5024976 *||Jul 23, 1990||Jun 18, 1991||Kennametal Inc.||Alumina-zirconia-silicon carbide-magnesia ceramic cutting tools|
|US5123935 *||Feb 22, 1990||Jun 23, 1992||Kabushiki Kaisha Kobe Seiko Sho||Al2 o3 composites, process for producing them and throw-away tip made of al2 o3 composites|
|US5254142 *||Jan 21, 1992||Oct 19, 1993||Sandvik Ab||Whisker reinforced composites for cutting tools with improved performance|
|US5264297 *||Apr 1, 1992||Nov 23, 1993||Kennametal Inc.||Physical vapor deposition of titanium nitride on a nonconductive substrate|
|US5858181 *||Aug 25, 1993||Jan 12, 1999||Kennametal Inc.||Physical vapor deposition of titanium nitride on a nonconductive substrate|
|US6610113||May 22, 2000||Aug 26, 2003||Kennametal Pc Inc.||Process for heat treating ceramics and articles of manufacture made thereby|
|US6737010||Oct 25, 2001||May 18, 2004||Kennametal Pc Inc.||Process for heat treating ceramics|
|US6988858||Feb 28, 2001||Jan 24, 2006||Kennametal Inc.||Oxidation-resistant cutting assembly|
|US7968182||Apr 17, 2006||Jun 28, 2011||Sandvik Intellectual Property Ab||Coated insert|
|US20020105116 *||Oct 25, 2001||Aug 8, 2002||Mehrotra Pankaj K.||Process for heat treating ceramics and articles of manufacture made thereby|
|US20020119017 *||Feb 28, 2001||Aug 29, 2002||Gates Alfred S.||Oxidation-resistant cutting assembly|
|US20040026813 *||Jun 26, 2003||Feb 12, 2004||Mehrotra Pankai K.||Process for heat treating ceramics and articles of manufacture made thereby|
|US20060257691 *||Apr 17, 2006||Nov 16, 2006||Sandvik Intellectual Property Ab||Coated insert|
|WO1993016647A1 *||Feb 8, 1993||Sep 2, 1993||Synvasive Technology, Inc.||Surgical cutting block and method of use|
|U.S. Classification||501/89, 51/309|
|International Classification||C04B35/119, C04B35/111, C04B35/645, C04B35/80|
|Cooperative Classification||C04B35/645, C04B35/111, C04B35/119, C04B35/803|
|European Classification||C04B35/80B, C04B35/645, C04B35/111, C04B35/119|
|Nov 3, 1988||AS||Assignment|
Owner name: KENNAMETAL INC., A CORP. OF COMMONWEALTH OF PA., P
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:MEHROTRA, PANKAJ KUMAR;REEL/FRAME:005002/0923
Effective date: 19881103
|Jan 5, 1989||AS||Assignment|
Owner name: KENNAMETAL INC., A CORP. OF PA, PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BILLMAN, ELIZABETH R.;REEL/FRAME:005002/0955
Effective date: 19881109
|Jul 28, 1992||CC||Certificate of correction|
|Mar 29, 1994||FPAY||Fee payment|
Year of fee payment: 4
|Mar 27, 1998||FPAY||Fee payment|
Year of fee payment: 8
|Oct 24, 2000||AS||Assignment|
Owner name: KENNAMETAL PC INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KENNAMETAL INC.;REEL/FRAME:011052/0001
Effective date: 20001023
|Mar 28, 2002||FPAY||Fee payment|
Year of fee payment: 12